Stabilized vitamin composition and method of making same



United States Patent 3,186,989 STABILEZED WTAMHN C(BREOSITIGN AND R LETHQD 0F MAKKNG SAW Grayce E. McMurtry, New York, N.Y., and John .l. Marvinny, Jersey City, NJ. No Drawing. Filed Apr. E2, 1961, Ser. No. 122,602 15 Claims. (Cl. 1678l) The present invention relates to the stabilization of vitamins against loss in potency. It is particularly concerned with vitamin A compositions which have high potency and which are suitable for addition to animal feeds and which will retain vitamin potency for long periods of time.

. The present joint application is a continuation-in-part of our abandoned application Serial No. 740,213, filed June 6, 1958.

Vitamin A, whether in pure form, ester form or other well-known forms, is subject to rapid loss in vitamin potency upon storage unless it is suitably stabilized. Many Well-known materials which are commonly used for stabiliz-ation of fats, such as oil-soluble amines, citric acid esters, phenolic anti-oxidants, etc. have been proposed for the stabilization of vitamin A concentrates, such as concentrates obtained from fish liver oils and the like. All of such materials heretofore proposed and combinations of them, While improving stability of vitamin concentrates still permit the concentrate to lose potency at a very substantial rate.

It is an object of the present invention to provide new compositions having a relatively high concentration of vitamin A, in which the vitamin A potency is maintained at a much higher level than heretofore obtainable.

It is another object of the present invention to provide a vitamin concentrate in a form suitable for easy addition to animal feeds and in which the loss of vitamin A is exceedingly low.

It is another object of the present invention to provide a vitamin-containing food which is free from agents such as oil-soluble amines which may cause undesirable side effects and in which the vitamin A content is substantially retained over long periods of storage. 7

It is still another object of the present invention to provide a vitamin concentrate which may be sold in the form of flakes or powder for addition to animal feeds and which retains vitamin A potency over long periods of time.

Otherobjects of the present invention will be apparent from the following description of the invention and the appended claims.

We have found that the vitamin A is stabilized by fatty alcohol esters of long-chain fatty acids whether synthetic or natural, such for example as obtained from sperm oil and preferably by a combination of such esters with gela tin and/or urea. It is further intended that where the term sperm whale oil or sperm oil is used, that it is intended to cover all fatty alcohol esters of the same general type if derived from natural or manufactured sources, as well as the fatty alcohols or their esters and/or fatty alcohols derived from vegetable sources. These fatty alcohol esters are surprisingly effective even alone. They are preferably but not necessarily hydrogenated to increase their hardness and softening point and are esters of longchain monobasic acids and long-chain alcohols. They are non-toxic. There is a synergistic action between the nitrogen-containing gelatin and/or urea and these fatty alcohol I esters which stabilize vitamin A in vitamin compositions in an almost unbelievable manner, The fatty acids may contain chemical unsaturation, i.e., carbon-to-earbon double bonds in either the alcohol or acid residue, or both. It is apparently not the unsaturation in these esters that provides the unique result, for it appears that the effect of hydrogenation is only to increase the melting point of the esters and facilitate formation of a flaky powder, which is most desirable. The long-chain alcohol residues and the long-chain acid residues in the fatty alcohol esters have 12 to 22 carbon atoms. Both the alcohols and acids from which these esters are formed are substantially linear, i.e., they are unbranched or have, if any, only a slight amount of branching, so that there is a linear chain of at least .12 carbon atoms in both the alcohol and acid residues of the esters.

A composition of the present invention preferablybut not necessarily contains besides natural or synthetic vitamin A, gelatin (and/or urea) and fatty alcohol esters, a separating agent having food value, such as the dried residue from skim milk, dextrin solution, corn syrup, brewers solubles, etc. which help keep spray dried particles from adhering together. 'If desired, suitable Wax may be incorporated to raise the melting point of the composition. Such wax is especially desirable when the fatty acid esters of fatty alcohols, such as obtained from the oil of seafaring mammals such as sperm Whale oil, are not hydrogenated and are therefore soft or low melting. Examples of such waxes which may be used to raise melting point and hardness are vegetable waxes such as carnauba wax, waxes obtained from petroleum such as microcrystalline wax, hydrogenated oils, fats or Waxes derived from glycerides, such as soy bean oil and tall oil, animal waxes, insect waxes such as beeswax, spermaceti wax, and combinations of the above-mentioned.

The fatty alcohol esters of fatty acids are generally used in the present invention in an amount substantially in ex cess of the amount of gelatin. However, the synergistic action of the gelatin and the fatty alcohol esters in preserving the vitamin potency of the material is so great that only a relatively small proportion of the gelatin, such as about 0.3 or 0.4% or so in relation to the total of gelatin plus fatty alcohol ester, and as much as 50 or 60% of gelatin in the synergistic vitamin-stabilizing mixture of gelatin and said esters may be present. Preferably, the amount of gelatin is about 2% to about 8 or 10% of this mixture. The vitamin A concentration in the composition may of course vary as Widely as desired, but in a concentrate for addition to feeds it is generally 1% to 10 or 12% of the said ester-gelatin mixture. The power separating agents which are nontacky when dried are of course added in the proportions desired, but in the final composition these nontacky, dried, Water-soluble or dispersible solids are preferably maintained between /2% and 25% of the weight of the composition.

The preferred method of combining the ingredients of the vitamin compositions of the present invention is to prepare a fluid dispersion or solution (preferably an aqueous dispersion or solution) of a natural or synthetic vitamin A concentrate (including vitamin A, esters, etc.), gelatin (and/or urea) and a dispersion or solution (preferably aqueous) of separating agent, such as corn syrup, skim milk, etc. This mixture is then spray dried to eliminate the fluidizing agent (volatile solvent or Water) and to form a powder containing the vitamin A concentrate. The dried separating agent, such as corn syrup, skim milk, dextrin, etc. greatly facilitates the maintenance of this mixture in powder form for easy blending into the fatty alcohol esters. It is conveniently present in amount of about 4 or 5% to 30 or 35% of the solids in the fluid solution or dispersion. The powder thus obtained containing the vitamin A in concentrated form may then be mixed into the melted sfatty alcohol ester or mixture of fatty alcohol ester and wax, which preferably also contains antioxidants or preservatives that may be desirable. The'melted mixture may then be sprayed or flaked at a temperature above its melting point and j hardness'of thecomposition.

preferably below 200 F. and usually between 150 and I 190 C. to obtain the composition of the present invention in the powder or flake form especially desirable for addition to feeds. V V

The following examples, in which parts are by weight, illustrate the preferred method of preparing compositions of the present invention.

EXAMPLE 1 About 30 parts of natural or synthetic vitamin A,

parts of gelatin, parts of corn syrup or skim milk;

parts'b y weight of water are formed into a solution or dispersion in water at a temperature of 130 to 190 F. The solution thus obtained is spray dried to obtain a dry powder consisting of of vitamin A, 25% of gelatin, and 25% of corn syrup solids or skim milk solids which function as a particle separating agent as well as a food. The powder thus obtained is then thoroughly mixed into a 'melted mixture of (1) 84.1 parts by weight of Hywax 120, which is a trade name for hydrogenated 190 F. to obtain the stabilized feed additiveof the present invention in powder form.

In the above example, 'th e vitamin A in the initial, aqueous solution or dispersion is usually maintained within 10 and parts and it may be substituted in whole or in part by fish liver oil containing the vitamins or by vitamin A acetate, palmitate, etc. aqueous dispersion is preferably held between 4 or 5 and 35 parts. The corn syrup or skim milk may be present between 4 or 5 and 35 parts. Between about 3'5" and or parts of water is usually used in order'to most convenient'ly form the powder for addition to the melted fatty alcohol ester; The product produced by spray drying the aqueous mixture is preferably between 1 and 25% of the final composition. 1 p p The antioxidants used may be omitted or substituted 7 4 mixed into chick feed to form the feed having the concentrations of vitamin A shown in the Table I. Day-old, sexed cockerel White Rock chicks were randomly distributed twenty per lot, into five lots. The birds were housed in a Jamesway electrically heated battery brooder with raised wire floors. and these weights with the levels of supplementation l and a copy of the basal ration are given in the following The gelatin in said J table. Atfive weeks of age, the birds were sacrificed and each lot subdivided into Lots A'and B. The livers of these sublots were pooled and run for their vitamin'A content. These liver values are also given in the Table I.

Table l Treatment 7 Lot Units/gm. Units/liver Ave.,

' units/liver Negative control USP oil, 2,000'unitsllb.{% 21 s? oil, 4,000 units/lb. {g v V a Sample 211, 2,000 A 5 V umtsllbf "{B 33.2 ass Sample 2H, 4,000 A 151 0 2 240 v "nits/1b "{B 210.0 21560 Meth0d.Ames, Risley and Harris, Anal. Chem., 26,

137 9 (1954). All twenty chicks in control lot were dead before five weeks.

EXAMPLE 3 v A sample ofvitamin A, which was prepared in accord- V ance with Example '1 above and labeled 2H, was submitted' to aresearch laboratory of a large alumni research foundation of a midwestern university for deter mination of vitamin A potency after aging. In accordance with the test, the sample was'assayed for vitamin A potency before mixing into the feed. Fivepounds of commercial rations were fortified to give units per gram basedton' the vitamin A assay. .USP reference standard oil of 100,000 units per gram was mixed into 7 5 pounds of the same commercial ration andusedas the control. Each mix was assayed forvitamin A in duplicate. 10 grams samples were placed in a 37 C. incubator and reassayed for vitamin A at two and at four .weeks. The results are given in the following table:

Table'll J i 0 time Two weeks 7 Fourweeks l i Ave. 7 Ave; Units/gmv Ave. Units/gm. percent Units/gm, percent ret. ret.

samp1e2H 113; 106 71 10" 95;s1;93 84L5 94;9s;95 USP Ref. oil 101; 102 I 102 67; 73; 70 058.6 45; 44; 45 44.1

in whole or'in part by other antioxidants recognized as notharmful in food. The hydrogenated rf'atty alcohol esters may be substituted by the nonhydrogenated fatty alcohol esters from. sperm whale oil. or from oil of seafaring mammals, without lossof stabilizing action. How- :ever, in such a case, it is preferred that a higher melting wax, such as one ormore of those before mentioned,

be also mixed with said fatty alcohol esters to increase A LEXAMPL E Z Q I 'The product prepared in Example 1, labeled Sample 2H,? was submittedto'a large midwestern university foundation laboratory for a chick liver storage study and j tested against, a negative control-land the customary vitamin A concentrate, aUSP. oil. The ingredients were V 44.1% in the USP'reference oil. This is anoutstanding. retention. Furthermore, the 'feed containing the sample 'It is seen from thejabovethat the per-cent retention even; after four weeks at this elevated temperature was' 86% of theoriginal vitamin concentration compared to f2H lost no potency atall after the two weeks of aging.

-:said esters to. ,value.

, When urea isusedin place of gelatin, we preferably dissolve the urea-inthe melted fatty alcohol Iesters; A icommercial product suchas Hywax 1 20 which'is the i Weekly weights were recorded hydrogenated fatty alcohol esters of fatty acids, derived from sperm whale oil is preferably used.

When the urea is completely dissolved in the fatty alcohol esters of fatty acids (derived from sperm whale tional experiments were also run, containing up to 25% urea, including some wherein other carriers such as Moby Dick Wax 95% were used in place of the hydrogenated Hywax 120 of formulations 4, 5, 6, 7, 8 shown oil), fish liver oil containing vitamin A is blended. The re- 5 in Table III. Moby Dick Wax 95% is a trade name for suiting formula can be molded into blocks, extruded, a wax whose source is from the sperm whale and compulverized, ground, flaked or spray chilled and packaged prises fatty alcohol esters of fatty acids from the oil for shipment or added to feed. thereof and has properties similar to those of the Hywax The fish liver oil employed may be the commercial 120. The results of all experiments run proved convariety containing multiple units of vitamin A per gram clusively that the presence of urea in amounts up to ap- (USP XIV), a synthetic crystalline vitamin A, such as proximately 25%, increased the retention to a marked palrnltate, acetate, or a vitamin A containing oil or subdegree as compared to the 100% fish liver oil (Example stance from another source. The range of potencies 9), and that urea in combination with any of the tested that were used for our experiments were from 200,000 to types of fatty alcohol esters of fatty acids derived from 400,000 units per gram, but we do not wish to be limmarine mammals was even more eifective in retaining lied on range of potencies. such potency.

The following six examples showing the range of per- The composition may contain, in addition to the essencentage of urea that may be employed in the compositial ingredients as indicated above, also other ingredients, tion are from 0.25% to From tests We have asas example, Various yp 111 Order to lcgrtained that the Preferred range is from to 20 fluence the hardness, and melting point to the composiurea and the greater retention of vitamin potency in the such Waxes known for thls PUIPOSe and form formulations is obtained whim a percentage of from 3% no part of the present invention. Examples of such waxes which may be used In this manner are: (1) Vegetable to 5% urea is utilized. h b 2 t Employing a recognized method of vitamin A analysis i i gi i g s a Z g i fi f and incouporating the feed supplement in a highly min- 25 y r n We 0 men 111 ape to 7 4 d tor d at C to accelerate reduction in industry, (3) hydrogenated oils, fats or waxes as derived era lze mlx s F L from glycerides such as soybean oil and tallow, (4) anipotency of vitamin A, also commonly referred L0 as demal Waxes, (5) insect waxgs Such as beeswax, (6) smmtmn 9 vltamm Followmg are the results spermaceti wax and the combinations of the above menthe tests with respect to (4) a feed supplement employing 30 fionei no urea and tests 5, 6, 7, t g the marked mcl'ease Typical proportions found suitable are hereinafter set In retellilon 0f Vltamm A m blends frolfl 1% to 10% forth in Table IV as illustrative examples of compositions u W131 the results from 3% t0 3% and when containing Wax hardness and as contemplated by the no l-Iywax is employed. instant invention. I

Table IV Percentages by weight Formulation N0 7 s 9 10 11 12 13 14 15 16 INGREDIENT V 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Hywax 120- 72.0 30.0 30.0 72.0 Carnauba warn... 5.0 5.0 5.5 77.0 Moby Dick Wax 95 72.0 36.0 36.0 72.0 Microc-rystalline Wax, t

elting point, 190/195" 7 Paraffin wax Hydrogenated castor oil- Candelilla wax 5.0 .0 Beesw 5.0 Spermaceti wax 77. 0

Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0

TableIIl It is to be understood that the proportions given in the above formulations, both in Table III and Table IV 353 2 g gg gg Percent of may be varied considerably, with and without ingredients Formulae value of after storage retention of other than those indicated herem as essential. SulttammA @ggfgg vitammA able proportions are from about 0.25% to about 25% urea by Weight, with a carrier (when used) preferably E containing the fatty alcohol esters of fatty acids derived x. 4. FLO ,20%, BK W 1 120,80 0 42,028 31, 521 75.0 from marine mammals sucn as from sperm whale O11, iigg%% fi 42,014 33779 8M about 5.0 to about 177% of a wax hardener, and the Ex. 6: FLO*,20%, Urea, balance comprising vitamin A such as fish liver oil congg 5 41568 taining natural vitamin A, also synthetic vitamin A such 5%;HY it; {9 3 42,268 39,521 as palmitate, and acetate and other vitamins whether i0 r r w1%"6j7 f 42,094 35,233 83,7 natural or synthetic. The wax hardener contents may be gs s g gggi;- varied with satisfactory results over wide limits, dependt5,,,,;, 13.0 ing upon the desired hardness and melting point desired.

One method of preparing the composition is as fol- Where initials FLO are used-this designates Fish liver oil," HY W 120 means "Hywax 120.

Table III shows the results of a few of the experiments which were run, and illustrates the marked increase-in retention of vitamin in compositions containing from zero urea content up to 10% urea content, by weight. Addilows: The fatty alcohol esters of fatty acids derived from marine mammals, such as from sperm whale oil or hydrogenated sperm whale oil, are first melted in a suitable container and heated to approximately C. The desired quantity of urea is then added to the melt,

at the above temperature or at varying lower or higher temperatures, While the melt is vigorously agitated. After the urea has been completely dissolved, the vitamin A,

in the form of fish liver oils orother forms such as synthetic and/or other vitamins is gradually added to the solution, while continually stirring. are then added, if desired, and the melted liquid is passed to conventional equipment for forming it into solid beaded or flaked particles in which form it is blended with feed ingredients. The flaked or beaded particles are usually packaged in paper or cloth bags or fibre containers.

In our application Serial No. 740,213, we pointed out that while the defined fatty alcohol esters of fatty acids such as thoseof hydrogenated sperm Whale oil had been used principally to demonstrate that these materials pro longed the potency of vitamin A, the invention could be used to prolong the potency of other vitamins contained in fish oil and any other vitamins suitable for inclusion in feed supplements. We, also, disclosed'that the defined fatty alcohol esters of fatty acids are preferably used in combination with urea for the stabilization of oilsoluble vitamins. V

i It is apparent that in accordance with the provisions of the patent statutes, modifications of the invention may be made wihout changing the spirit thereof. J Having described our invention, we claim:

1. A method of producing an improved feed supplement comprising a fish liver oil containing vitamin A and other synthetic and natural vitamins having a prolonged vitamin potency, comprising the steps of heating to above its melting point a composition containing essentially fatty alcohol esters of fatty acids derived from sperm whale oil, said fatty alcohol esters of fatty Hardening waxes V and from about 0.25% to about 25.0% by weight urea wherein the vitamins are stabilized. a

3. The composition according to claim 2 wherein the urea is present in an amount of from about 1% to about 10% by weight.

4. The composition according to claim 3 wherein there are included petroleum waxes.

5. The composition according to 7. The composition according to claim 2 wherein the acid ester is derived from sperm whale oil.

8. The composition according to claim 2, in which the ester is sperm whale oil containing essentially saturated fatty alcohol esters of fatty acids in solid, refined,

oil consists of fish liver oils andethe urea is present in acids containing from 12 to' 22 carbon atoms, adjusting said composition to a temperature of approximately 90 0., adding urea to said composition while stirring, continuing the stirring until the urea is completely dissolved, "adding fish 'liver'oil and additional vitamins, constantly stirring to a homogeneous mixture and preparing same for packaging, said urea being present in amounts of .25 to 25% of the weight of the ingredients in said feed supplement.

2. A feed supplement composition for animals comprising an oil solution of oil-solublev vitamins containing "vitamin A, an ester of'a fatty alcohol and a fatty acid,

wax form. r

9. The composition according to claim 2 whereinrthe an amount of from about 1% to about 10% by weight. 10. The composition according to claim 9 wherein the 'urea ispresent in an amount from about 3% to about 5% by weight.

11. The composition according to claim 7 wherein the oil consists'of fish liver oils.

12. The composition according to claim a wax hardener is present.

13. A feed supplement as set forth in claim 2, wherein the vitaminis present as a concentrate.

14. Thetcomposition 'as set forth in claim 2 wherein there is included gelatin.

15. The composition as set forth in claim 2 wherein part of the urea is substituted by gelatin;

11 wherein References Cited in the file of this patent V UNITED STATES PATENTS said alcohol and acid each containing 12 to 22 carbon atoms with at least 12 carbon atoms in a straight chain,

OTHER REFERENCES Jenkins: The Chemistry ofOrganic Medicinal Prod- 1 1cts, secondedition, 1941, John Wiley'and Sonsluc,

'London, pages 256-258.

claim 3 wherein there are included at least one member of the group consisting 

1. A METHOD OF PRODUCING AN IMPROVED FEED SUPPLEMENT COMPRISING A FISH LIVER OIL CONTAINING VITAMIN A AND OTHER SYNTHETIC AND NATURAL VITAMINS HAVING A PROLONGED VITAMIN POTENCY, COMPRISING THE STEPS OF HEATING TO ABOVE ITS MELTING POINT A COMPOSITION CONTAINING ESSENTIALLY FATTY ALCOHOL ESTERS OF FATTY ACIDS DERIVED FROM SPERM WHALE OIL, SAID FATTY ALCOHOL ESTERS OF FATTY ACIDS CONTAINING FROM 12 TO 22 CARBON ATOMS, ADJUSTING SAID COMPOSITION TO A TEMPERATURE OF APPROXIMATELY 90* C., ADDING UREA TO SAID COMPOSITION WHILE STIRRING, CONTINUING THE STIRRING UNTIL THE UREA IS COMPLETELY DISSOLVED ADDING FISH LIVER OIL AND ADDITIONAL VITAMINS, CONSTANTLY STIRRING TO A HOMOGENEOUS MIXTURE AND PREPARING SAME FOR PACKAGEING, SAID UREA BEING PRESENT IN AMOUNTS OF .25 TO 25% OF THE WEIGHT OF INGREDIENTS IN SAID FEED SUPPLEMENT. 